InP hierarchical microspheres with an average diameter of 1 μm self-assembled from nanodollops of about 200 nm were synthesized by the reaction of 2 mmol of InCl3 and 15 mmol of yellow phosphorus in ethanolamine–water binary solution at 170 °C for 12 h. Experiments show that the morphologies of the products were mainly affected by the reaction temperature and the quantities of reactants. The InP hierarchical microspheres prepared in our experiment could emit blue light, which probably correlates to the crystal defects.